Treatment of and developing composition for photographic light-sensitive materials

ABSTRACT

PHOTOGRAPHIC LIGHT SENSITIVE DEVELOPING COMPOSITIONS CONTAINING INOSITOLPOLYPHOSPHORIC ACID OR AN ALKALI METAL SALT OF INSOITOLPOLYPHOSPHORIC ACID TO PREVENT STAINING AND AERIAL FOG ARE DISCLOSED.

United States Patent Oflice 3,664,838 Patented May 23, 1972 US. CI.96-56 7 Claims ABSTRACT OF THE DISCLOSURE Photographic light sensitivedeveloping compositions containing inositolpolyphosphoric acid or analkali metal salt of inositolpolyphosphoric acid to prevent staining andaerial fog are disclosed.

BACKGROUND OF THE INVENTION Field of the invention This inventionrelates to a method of treatment of a photographic light-sensitivematerial, in particular, by the use of an improved developer.

Prior art It is well known that when a photographic light-sensitivematerial is treated with a developing solution containing a heavy metalion, for example, an iron ion or a copper ion, stains often occur. Thisis caused by many factors, for example, coloring by the reaction productof such heavy metal ion contained in a developer with a photographiclight-sensitive material, dyeing of a photographic light-sensitivematerial with the heavy metal ion itself and catalytic acceleration ofaerial fog by the'heavy metal ion. The contamination of a developer withheavy metal ions is mainly due to impurities from the water, theprocessing apparatus and the chemicals used. It is also known that adeveloping solution prepared from water containing large amounts ofcalcium ion and magnesium ion, for example, present in hard water, tendsto cause turbidity or precipitation.

It has been proposed, as is well known, in order to prevent suchstaining or precipitation to add to a developing solution a chelatingagent such as ethylenediaminetetraacetic acid (EDTA), nitrilotriaceticacid (NTA), 1,3-diamino-Z-propanoltetraacetic acid as disclosed inUnited States Pat. 2,875,049, or condensed polyphosphoric acid, forexample, as sold under the trade name of Calgon. However, this attemptis unsatisfactory because although the addition of the known chelatingagents to a developer results in a softening of hard water, the additiondoes not prevent stains. Furthermore, some of these chelating agentsaccelerate catalytically the oxidation of a developing agent thusshortening the life of the developing solution (see Photographic Scienceand Engineering 3, 49 (1959)), and accordingly, the use of chelatingagents is limited considerably.

It is further well known, on the other hand, that a color developercontaining, for example, N,N-diethyl-pphenylenediamine orN,N-diethyl-2-methyl-p-phenylenediamine, suffers deterioration andaerial fog often is encountered, since a large amount of sulfite cannotbe added thereto. Such deterioration or aerial fog can be considerablyreduced by adding an antioxidant such as hydroxylamine to a developerbut not completely eliminated. In addition, the use of a large amount ofan antioxidant such as hydroxylamine rather deteriorates thephotographic properties.

It is a principal object of this invention to provide a method oftreating a photographic light-sensitive material whereby the abovementioned disadvantages such as staining and fog formation can beovercome.

DESCRIPTION OF THE INVENTION A compound having very effective chelatingproperties to prevent stains formed during developing as well as veryeffective aerial fog inhibiting properties without being harmful tophotographic light-sensitive materials and developers over a wide rangeof addition amounts was sought. It was found that the foregoing objectcan be accomplished by adding an inositolpolyphosphoric acid or itsalkali metal salt to a developing solution. The inositolpolyphosphoricacid or its alkali metal salt used in this invention, being stable, isalso effective as hard water softeners and preservatives.

DETAILED DESCRIPTION OF THE INVENTION Addition of aninositolpolyphosphoric acid or its alkali metal salt to a developingsolution according to this invention results in the followingadvantages:

(1) Staining due to heavy metal ion (2) Aerial fog (3) Aerial fog due tothe catalytic effect of heavy metal ion (4) Hard water softening (5)Preservation of developer Illustrative of the inositolpolyphosphoricacids or their alkali metal salts used in this invention are thefollowing compounds:

Compound 1.Inositolhexaph0sphoric acid Compound2.-Inositolpentaphosphoric acid Compound 3.--Inositoltetraphosphoricacid Compound 4.9Na Inositolhexaphosphate Compound 5.--11NaInositolhexaphosphate Compound 6.7K Inositolhexaphosphate Theinositolpolyphosphoric acid or its alkali metal salt used in thisinvention can be synthesized in a conventional manner, for example, asdisclosed in Chemical Engineering, Jan. 27, 1958, p. 61.

The compound of this invention is added in a proportion of from 10 mg.to 10 g. for each 1000 ml. of a developing solution. Preferably from 0.1to 3 g. is used.

The inositolpolyphosphoric acid or its alkali metal salt of theinvention can be used together with the above described known compounds.

A developing solution containing the additive of this invention isapplicable to any photographic light-sensitive materials, in particular,color photographic lightsensitive materials, in particular, colorphotographic lightsensitive materials, containing the yellow couplerdescribed in United States Pat. 3,409,439 and British Pat. No.1,113,038, the magenta coupler described in United States Pat. 3,337,344and British Pat. No. 1,142,553 and the cyan coupler described in UnitedStates Pats. 2,423,730, 2,474,- 293, and 2,801,171 and thelight-sensitive material de scribed in French Pat. No. 1,576,417.

Typical examples wherein the inositolpolyphosphoric acid or its alkalimetal salt of this invention is added to a developing solution are givenin the following examples in order to illustrate the invention withoutlimiting the invention.

EXAMPLE 1 A color photographic printing paper having, on a baryta paperas a support, a blue-sensitive silver iodobromide emulsion layercontaining benzoylaceto-Z-chlorO-S- dodecyloxycarbonylanilide as ayellow coupler, a gelatin intermediate layers, a green-sensitive silverchlorobromide emulsion layer containing1-phenyl-3-[3-(N-butylcaprylamidepropionamide) ]--pyrazolone as amagenta coupler, a gelatin intermediate layer, a red-sensitive silverchlorobromide emulsion layer containing 1-hydroxy-2-[3-(2,4"-di-t-amyl-phenoxy)propyl]naphthamide as a cyan coupler and a gelatinprotective layer was treated with the developing solution described inThe British Journal of Photography, Sept. 27, 1968, p. 838, while addingthe compound of the invention or ferric sulfate for a comparison of thestain inhibiting property thereto, at 30 C. for 7 minutes.

Developer-l (Control): (pH 10.6) Sodium metaborate g 25.0 Sodium sulfiteg 2.0 Hydroxylamine (sulfate) g 2.0 Potassium bromide g 0.5 6nitrobenzimidazole (nitrate) g 0.02 Caustic soda g 4.0 Benzyl alcohol ml15.8 Diethylene glycol ml 20.0 N ethyl N beta methanesulfonamidoethylpphenylenediamine (sulfate) g 8.0

Water to 1000 ml.

Developer-2: 0.1 g. of ferric sulfate was added to 1000 ml. ofDeveloper-1.

Developer-3: 0.1 g. of ferricsulfate and 2 g. of Calgon (trade name)were added to 1000 ml. of Developer-l.

Developer-4: 0.1 g. of ferric sulfate and 2 g. of EDTA- 2Na were addedto 1000 ml. of Developer-1.

Developer-5 0.1 g. of ferric sulfate and 2 g. of NTA were added to 1000ml. of Developer-1.

Developer-6: 0.1 g. of ferric sulfate and 2 g. of Compound 1 were addedto 1000 m1. of Developer-l.

EDTA-2Na: disodium ethylenediaminetetraacetate.

NTA: nitrilotriacetic acid.

Developer-2 to Developer6 were also adjusted to pH 10.6.

Then, the color photographic material was subjected to the processing,i.e., stop fixing--washingbleaching-- washinghardenerfixingwashing--stabilizingdrying. The stop-fixing bath contains ammoniumthiosulfate, the bleaching bath contains potassium ferricyanide, thehardener fixing bath contains ammonium thiosulfate and formalin and thestabilizing bath contains sodium metaborate.

The following table shows the degree of staining when treated withDeveloper-1 to Developer-6. Since the stain formed by this treatment wasbrown, it was shown by the blue optical density on a non-exposed area.

Developer No.: Blue optical density As is evident from this table, thecolor developer containing ferric ion results in a large amount ofstaining, which can be inhibited completely by adding Compound 1. Whencommercially available color films and color printing papers weretreated also, similar results were obtained.

EXAMPLE 2 A color light-sensitive material having, on an acetate filmsupport, a blue-sensitive silver iodobromide emulsion layer containing ayellow coupler, a gelatin intermediate layer, a red-sensitive silverchlorobromide emulsion layer containing a cyan coupler, a gelatinintermediate layer, a green-sensitive silver chlorobromide emulsionlayer containing a magenta coupler and a gelatin protective layer wastreated at 21 C. for 12 minutes with the developing 4 solution describedin Journal of the SMPTE 61, 12, 667

"(1953) and with the same solution but to which the compounds of thisinvention were added.

Developer-7: (pH 10.65) g. Calgon (trade name) 2.0 Sodium sulfite 4.0

N,N-diethyl p phenylenediamine (hydrochloride) 3.0 Sodium carbonate(monohydrate) 20.0 Potassium bromide 2.0

Water to 1000 ml.

Developer-8: 2 g. of hydroxylamine (hydrochloride) was added to 1000 ml.of Developer-7.

Developer-9: 1 g. of Compound 1 was added to 1000 ml.

of -Developer7.

Developer-10: 1 g. of Compound 4 was added to 1000 ml.

of Developer-7.

Developer-11: 1 g. of Compound 5 was added to 1000 ml.

of Developer-7.

Developer-l2: 1 g. of Compound 6 was added to 1000 ml.

of Developer-7. l

Developer-8 to Developer-12 were also adjusted to pH of 10.65.

The treatment was carried out in the order of prebath rinse developmentrinse fixing washing leaching washing fixing washing -stabilizingdrying. The prebath contained caustic soda and the bleaching bathcontained potassium dichroir iate. The other baths were similar to thoseof Example 1.

The following table shows the degree of fog formed when treated withDeveloper-7 to Developer-12. This treatment was carried out using atray. The aerial fog appearing in any of the cyan, magenta and yellowlayers, particularly strong in the cyan layer, is represented by the redoptical density on a non-exposed area.

Developer No.: Red optical density As is evident from this table', thecolor developer containing no antioxidant produced a market aerial fog.In using Developer-8, there was a considerable air for inhibiting effectbut not so suflicient and the sensitivity was less than in usingDeveloper-7. On the contrary, Developer-9 to Developer-l2 containing theadditives of the invention was substantially free from aerial fog, hadno influence upon the photographic properties and was so stable thatdecomposition did not occur.

When commercially available color films and color printing papers weretreated in the above manner, similar results were obtained.

EXAMPLE 3 A photographic printing paper having a silver chlorobromideemulsion layer on baryta paper was treated at 20* C. for seconds witheach of the following Developer-l3 to Developer-16.

Developer-l3: I G. Metol (trade name) 1.0 Sodium sulfite 15.0Hydroquinone 4.0 Sodium carbonate (monohydrate) 27.0 Potassium bromide0.7

Water to 1000 ml.

Developer-14: 0.2 g. of ferric sulfate' was added to 1000 m1. ofDeveloper-13.

Developer-15: 0.2 g. of ferric sulfate and 0.5 g. of Compound 1 wereadded to 1000 m1. of Developer-13.

Developer-16: 0.2 g. of ferric sulfate and 0.5 g. of Compound 3 wereadded to 1000 ml. of Developer-'13.

Developer N0.: I Blue optical density 13 ..a 0.03 14 0.10

As is evident from this table, the developer containing ferric ionresults in a high degree of staining, which can be inhibited completelyby adding Compound 1 or Compound 3.

When commercially available film and printing papers were treated inthis manner, similar results were obtained.

What is claimed is:

1. A method of developing an exposed photographic light-sensitive silverhalide material which comprises de- Veloping said material in adeveloper containing a compound selected from the group consisting of aninositolpolyphosphoric acid and an alkali metal salt thereof.

2. The method according to claim 1 wherein said compound contained insaid developer is selected from the group consisting of a sodium salt ofinositolpolyphosphoric acid and a potassium salt ofinositolpolyphosphoric acid.

3. The method according to claim 1 wherein said compound contained insaid developer is selected from the group consisting ofinositolhexaphosphoric acid, inositolpentaphosphoric acid,inositoltetraphosphoric acid, 9Na inositolhexaphosphate, 11Nainositolhexaphosphate and 7K inositolhexaphosphate.

4. The method of developing an exposed color photographiclight-sensitive silver halide material which comprises developing saidmaterial in a color developer containing a compound selected from thegroup consisting of an inositolpolyphosphoric acid and an alkali metalsalt thereof.

5. The method of developing an exposed black and white light-sensitivesilver halide material which comprises developing said material in ablack and white developer containing a compound selected from the groupconsisting of an inositolphosphoric acid and an alkali metal saltthereof.

6. In a composition for developing a photographic light-sensitive silverhalide material which comprises a developing agent and an alkali, theimprovement which comprises said composition containing a compoundselected from the group consisting of an inositolpolyphosphoric acid andan alkali salt thereof.

7. In a color developer composition for developing a color photographiclight-sensitive silver halide material which comprises a colordeveloping agent and an alkali, the improvement which comprises saidcomposition containing a compound selected from the group consisting ofan inositolpolyphosphoric acid and an alkali salt thereof.

References Cited UNITED STATES PATENTS 2,875,049 2/1959 Kridel 9666.4

NORMAN G. TORCHIN, Primary Examiner E. C. KIMLIN, Assistant Examiner US.Cl. X.R. 9 666

